EP0457354B1 - Verfahren zur Herstellung von alkalischen Zinkbatterien - Google Patents

Verfahren zur Herstellung von alkalischen Zinkbatterien Download PDF

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Publication number
EP0457354B1
EP0457354B1 EP91108064A EP91108064A EP0457354B1 EP 0457354 B1 EP0457354 B1 EP 0457354B1 EP 91108064 A EP91108064 A EP 91108064A EP 91108064 A EP91108064 A EP 91108064A EP 0457354 B1 EP0457354 B1 EP 0457354B1
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European Patent Office
Prior art keywords
indium
zinc alloy
hydroxide
indium hydroxide
sulfide
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EP91108064A
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English (en)
French (fr)
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EP0457354A1 (de
Inventor
Hiroshi Yoshizawa
Akira Miura
Yoshiaki Nitta
Sachiko Sugihara
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP12848490A external-priority patent/JPH0697611B2/ja
Priority claimed from JP12847990A external-priority patent/JPH07107857B2/ja
Priority claimed from JP12848290A external-priority patent/JPH07107858B2/ja
Priority claimed from JP12848090A external-priority patent/JP2808822B2/ja
Priority claimed from JP2128485A external-priority patent/JP2754865B2/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0457354A1 publication Critical patent/EP0457354A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method of manufacturing mercury-free zinc-alkaline batteries comprising zinc as an anode active material, an aqueous alkaline solution as an electrolyte, manganese dioxide as a cathode active material, silver oxide, oxygen, etc., which batteries have no adverse effect on environment and have an excellent shelf stability and discharge property.
  • Indium is known as a high hydrogen-overvoltage additive material for the anodes of secondary batteries as well as primary batteries.
  • U.S. Patent Nos. 4,735,876, 4,861,688 and 4,920,020, and Japanese Patent KOKOKU (Post-Exam. Publn.) No. Hei 2-22984 disclose methods of using the elements as the alloying additives; Japanese Patent KOKOKU (Post-Exam. Publn.) No. Sho 51-36450, Japanese Patent KOKAI (Laid-Open) No. Sho 49-93831, Japanese Patent KOKAI (Laid-Open) No. Sho 49-112125 disclose methods of adding indium oxide and indium hydroxide as the inorganic inhibitor; and Japanese Patent KOKAI (Laid-Open) No. Hei 1-105466 discloses a method of adding a mixture of indium oxide and cadmium oxide. Furthermore, Japanese Patent KOKAI (Laid-Open) Nos. Sho 61-96666 and 61-101955 disclose adding these elements as additives to the anodes of secondary batteries.
  • U.S. Patent No. 3,847,669 proposes ethylene oxide.
  • U.S. Patent No. 4,195,120 discloses organic phosphate esters of the ethylene oxide-adduct type
  • U.S. Patent No. 4,606,984 discloses perfluorate organic compounds of the ethoxylated fluoro alcohol type.
  • Japanese Patent KOKAI Lithoxylated fluoro alcohol type
  • the object of the present invention is to provide a method of manufacturing zinc-alkaline batteries free of environmental destruction and having an improved resistance to electrolyte-leak and a good storage stability.
  • these batteries are manufactured by incorporating a zinc alloy having an appropriate composition and indium hydroxide or indium sulfide synthesized to have suitable properties by an appropriate method, into a gel-like alkaline electrolyte.
  • the zinc-alkaline batteries having an inside pressure of battery inhibited from being raised by generation of gas due to the corrosion reaction can be obtained even without mercury by incorporating the zinc alloy having an appropriate composition and the indium hydroxide or indium sulfide synthesized to have suitable properties by an appropriate method and further incorporating an organic inhibitor.
  • Fig. 1 is a half cross-sectional view of an alkaline manganese battery in an example of the present invention.
  • the present inventors have studied on the most effective materials of the corrosion resistant zinc alloys, inorganic inhibitors and organic inhibitors, respectively, and the optimum added state and amounts of the materials.
  • the use of the corrosion-resistant zinc alloy in combination with the inorganic inhibitor in accordance with the present invention will be elucidated below.
  • the gel-like anode used in the present invention is constituted by a gel-like alkaline electrolyte comprising a corrosion-resistant zinc alloy powder as an active material and containing an indium hydroxide powder having suitable properties dispersed therein in an appropriate concentration, the zinc alloy consisting of an appropriate amount of one or more selected from the group consisting of indium, lead, bismuth, lithium, calcium and aluminum and the balance of zinc.
  • the gel-like anode used in the present invention is constituted by a gel-like alkaline electrolyte comprising a corrosion-resistant zinc alloy powder as an active material, which contains an indium hydroxide powder having suitable properties dispersed therein in an appropriate concentration and further a so-called perfluoroalkyl polyethylene oxide surfactant as the organic inhibitor added thereto in an appropriate amount, the perfluoroalkyl polyethylene oxide having the hydrophilic part of polyethylene oxide and the oleophilic part of a fluoroalkyl group and the zinc alloy consisting of an appropriate amount of one or more selected from the group consisting of indium, lead, bismuth, lithium, calcium and aluminum and the balance of zinc.
  • the zinc alloy contains 0.01-1 wt% of indium and 0.005-0.5 wt% in total of one or more of lead and bismuth, or 0.01-1 wt% of indium, 0.005-0.5 wt% of one or two of lead and bismuth and 0.005-0.2 wt% in total of one or more of lithium, calcium and aluminum.
  • the indium hydroxide used herein is preferably synthesized by neutralizing an aqueous solution of indium chloride or indium sulfate as starting substance.
  • the use of the indium chloride as starting substance can produce the indium hydroxide having a better corrosion resistance than the use of the indium sulfate.
  • the aqueous solution of them to be neutralized should contain chloride ions in order to effectively produce the indium hydroxide.
  • the indium hydroxide is preferably in a powdery form, which contains at least 60 wt%, preferably at least 70 wt% of particles having a particle size of 0.5-8 »m and a weight loss of 18-30 wt%, preferably 20-25 wt% when thermally decomposed at a temperature of up to 900°C.
  • the indium hydroxide effectively has a powdery X-ray diffraction pattern having broad peaks at 4.71 ⁇ 0.10 ⁇ , 3.98 ⁇ 0.02 ⁇ 3.57 ⁇ 0.10 ⁇ , 2.66 ⁇ 0.02 ⁇ Further, the appropriate amount of the indium hydroxide added is in the range of 0.005 to 0.5 wt% based on the weight of the zinc alloy.
  • the amount of the abovementioned perfluoroalkyl polyethylene oxide surfactant added to the alkaline electrolyte is effectively in the range of 0.001 to 0.1 wt% based on the weight of the zinc alloy.
  • the chemical structure of the surfactant has the formula of (X)-C n F 2n -(Y)-(CH2CH2O) m -(Z) wherein X is -H or -F, Y is -C2H4-O-CH2CH(OH)-CH2O-, -CONH- or -SO2NR-, wherein R is -H or an alkyl group, Z is -CH3, -PO3W2 or -SO3W, wherein W is an alkali metal, n is 4 to 10 and m is 20 to 100, or the formula of (X)-C n F 2n -(CH2CH2)-(CH2CH2O) m -(Z) wherein X is -H or
  • indium, lead and bismuth themselves have a high hydrogen overvoltage and hence raise the hydrogen overvoltage of the surface of the zinc alloy when added to the zinc alloy.
  • the function of the elements raising the hydrogen overvoltage is maintained even when a fresh surface of the zinc alloy appears during the discharging, if the elements are uniformly dispersed in the body of the zinc alloy.
  • lithium, aluminum and calcium have a function of sphering zinc grains to reduce the true specific surface area of the zinc grains so that the amount of the zinc alloy corroded per unit weight is decreased.
  • the indium hydroxide powder When the indium hydroxide powder is dispersed together with the zinc alloy into the gel-like alkaline electrolyte, part of the indium hydroxide is electrodeposited onto the surface of the zinc alloy through the principle of the substitution plating, thereby raising the hydrogen overvoltage on the surface.
  • the remaining part of the indium hydroxide is retained as it is in a solid form in the gel-like alkaline electrolyte, and this part is to be electrodeposited onto a fresh surface of the zinc alloy exposed when subjected to discharging, thereby allowing the zinc alloy to remain to be corrosion resistant.
  • the limitation of the weight loss of the indium hydroxide when thermally decomposed depends upon the crystallinity thereof.
  • the solubility of the indium hydroxide powder varies depending upon the weight loss. If the weight loss by the thermal decomposition is too small, then the solubility is lowered, and if the weight loss is too large, then the solubility is raised.
  • the properties of the indium hydroxide vary depending upon methods of synthesizing the indium hydroxide.
  • the indium hydroxide synthesized from indium chloride and indium sulfate as starting materials has a crystallinity and crystal shape giving such an excellent corrosion resistance as mentioned above.
  • the use of indium chloride as starting material produces much better indium hydroxide than the use of indium sulfate.
  • the synthesis of an indium hydroxide having the same properties as those of the indium hydroxide synthesized from indium chloride as starting material is possible with indium nitrate and indium sulfate as starting materials by neutralizing in the presence of chloride ions.
  • the surfactant When the surfactant is present in the alkaline electrolyte together with the zinc alloy, it is chemically adsorbed on the surface of the zinc alloy through the metal soap principle to form a hydrophobic monomolecular layer which exhibits the corrosion-inhibiting effect.
  • the surfactant having polyethylene oxide at the hydrophilic portion thereof is highly soluble in a micell form in the alkaline electrolyte. Therefore, the surfactant rapidly transfers to and is immediately adsorbed on the surface of the zinc alloy, when it is charged into the electrolyte. This means that the surfactant provides a high corrosion resistance to the zinc alloy.
  • the greater the polymerization degree of the polyethylene oxide the higher the solubility of the surfactant.
  • the polymerization degree is desirably 20 or more.
  • the terminal group is preferably methyl group, sulfone group or phosphate group which is highly resistant to alkalis. If the oleophilic portion of the surfactant has a fluoroalkyl group, the group effectively prevents receiving and donating of electrons which causes the corrosion reaction, when the group is adsorbed on the surface of the zinc alloy. This is because the group is highly electrically insulating.
  • the bond between the hydrophilic group and the oleophilic group preferably has a hydrophilic ether bond and hydroxyl group, rather than the water-repelling alkyl group, because the ether bond and hydroxyl group bond more easily to the zinc alloy, so that the surfactant provides higher corrosion resistance.
  • the advantages by the combination of the zinc alloy and the indium hydroxide will be elucidated below. Since the indium hydroxide is electrodeposited to work on the surface of the zinc alloy, the electrodeposition is needed to be effected smoothly and evenly. Since a large amount of hydrogen gas is generated on the surface of the zinc alloy having no corrosion resistance, the electrodeposition of indium is prevented, so that the electrodeposition is made uneven. However, the generation of hydrogen gas is inhibited on the surface of the corrosion-resistant zinc alloy, so that the electrodeposition is effected smoothly and evenly to obtain the desired combination advantages. These advantages are obtainable even after partial discharging.
  • the corrosion-resistant zinc alloy powder is made by a so-called atomizing method in which zinc of 99.97% in purity is molten, predetermined additive elements are added in predetermined amounts to the melt, the melt is rendered uniform and then the melt is atomized by compressed air. The resulting particles are classified to be within the range of 45-150 mesh.
  • the indium hydroxide is synthesized by adding a saturated amount of a predetermined indium salt to ion-exchange water, rapidly neutralizing the resulting aqueous solution with ammonia gas as a neutralizing agent under stirring with a screw stirrer by adding the ammonia gas to the solution until the pH of the solution becomes 9, then washing the precipitate on a filter having a mesh size of 0.5 »m with ion-exchange water until the pH of the filtrate becomes 7.5, separating the water content from the precipitate by making vacuum underneath the filter and drying the precipitate under vacuum at a relatively low temperature of 60°C.
  • the indium hydroxide has a powdery X-ray diffraction pattern having broad peaks at 4.71 ⁇ 0.10 ⁇ , 3.98 ⁇ 0.02 ⁇ , 3.57 ⁇ 0.10 ⁇ and 2.66 ⁇ 0.02 ⁇ .
  • the indium sulfide is synthesized by adding a saturated amount of a predetermined indium salt to ion-exchange water, rapidly neutralizing the resulting aqueous solution with hydrogen sulfide as a neutralizing agent under stirring with a screw stirrer by adding the ammonia gas to the solution until the pH of the solution becomes 9, then washing the precipitate on a filter having a mesh size of 0.5 »m with ion-exchange water until the pH of the filtrate becomes 7.5, separating the water content from the precipitate by making vacuum underneath the filter and drying the precipitate under vacuum at a relatively low temperature of 60°C.
  • the gel-like anode is prepared in such a manner as described below.
  • a 40% potassium hydroxide aqueous solution also containing 3 wt% of ZnO
  • 3 wt% of sodium polyacrylate and 1 wt% of carboxymethyl cellulose to form a gel-like electrolyte.
  • To the gel-like electrolyte is gradually added a predetermined amount of an indium hydroxide or indium sulfide powder under stirring.
  • the electrolyte is then aged for 2-3 hours.
  • the zinc alloy powder is mixed with the aged gel-like electrolyte in such a weight ratio that the amount of the former is two times larger than that of the gel-like electrolyte.
  • a predetermined amount of the inhibitor is added to the gel-like electrolyte prior to adding the indium hydroxide during the abovementioned preparation of the indium hydroxide.
  • Fig. 1 is a cross-sectional view of the LR 6 alkaline manganese battery used in the example of the present invention.
  • reference number 1 denotes a cathode compound
  • 2 a gel-like anode featuring the present invention
  • 3 a separator
  • 4 a current collector of the gel-like anode
  • 5 a cathode terminal cap
  • 6 a metal case
  • 7 an outside housing of the battery
  • 8 a polyethylene-made resin plug for closing the opening of the case 6, and 9 a bottom plate forming the anode terminal.
  • This example is an embodiment using the combination of a zinc alloy and an inorganic inhibitor.
  • Table 1 shows the results of the leak test for batteries made from the corrosion-resistant zinc alloys as mentioned above with changed amounts of indium hydroxide added. The leak test was carried out with the batteries stored at 60°C for 30 days.
  • Table 2 shows the results of the leak test for batteries prepared from the corrosion-resistant zinc alloys as mentioned above with changed amounts of indium sulfide added. The leak test was carried out with the batteries stored at 60°C for 60 days.
  • the indium sulfide is hydrolyzed in the alkaline electrolyte to form indium hydroxide and sulfur. This sulfur is reacted with zinc to give anticorrosion. Therefore, an alkali metal sulfide and indium hydroxide may be used in combination to obtain the same effect.
  • the amount of the alkali metal sulfide added is preferably in the range of 0.002 to 0.2 wt% based on the weight of the zinc alloy.
  • Table 3 shows the results of the leak test for batteries prepared using an unchanged indium hydroxide amount of 0.1 wt% and changed amounts of the alloying additives. The leak test was carried out with the batteries stored at 60°C for 30 days.
  • the amounts of additives added to the zinc alloy are suitably in the range of 0.01 to 1 wt% for indium, 0.005 to 0.5 wt% for each or two of lead and bismuth, or 0.005 to 0.2 wt% for each or two of calcium and aluminum. Furthermore, the same effect may be obtained by substituting lithium for the aluminum.
  • This example employed an indium hydroxide prepared by neutralizing an aqueous solution of indium sulfate as the starting material. Similar effect may be obtained by employing an indium hydroxide prepared by using indium chloride or indium nitrate. The higher effect was obtained by using each indium hydroxide prepared with the chloride, sulfide and nitrate as the starting material in this order.
  • This example elucidates the effect of the starting materials for preparing the indium hydroxide in the combination of the zinc alloy and the inorganic inhibitor.
  • Table 4 shows the results of leak test for batteries using 0.1 wt% based on the weight of the zinc alloy of indium hydroxide prepared from various starting materials. The leak test was carried out with the batteries stored at 60°C for 45 days.
  • indium hydroxide from the nitrate is effective if it is prepared in the presence of chloride ions. That is, a battery with indium hydroxide prepared from the nitrate as starting material had a leak index of 0% even after storing at 60°C for 30 days, which revealed that the battery is of practical use. However, it is seen that indium hydroxide from the chloride or sulfate as starting material is more reliable for a longer period since a battery with the indium hydroxide had a leak index of 0% after storing at 60°C for 45 days.
  • Table 5 shows the results of leak test with batteries using indium hydroxide powders having various particle size distributions.
  • the indium hydroxide powders were added in an amount of 0.1 wt% based on the weight of zinc alloy.
  • the leak test was carried out with the batteries stored at 60°C for 45 days.
  • an indium hydroxide powder is preferred to contain 60 wt% or more of particles of 0.5 to 8 »m in size (the balance is particles having a size of 0.5 »m or larger, because the powder on a filter having a mesh of 0.5 »m was washed with water). There may be such a case that batteries with 70 wt% or more of the particles do not leak any amount of electrolyte even after storing at 60°C for 60 days.
  • the indium hydroxide used in this example was one prepared with indium nitrate as starting material and obtained through the classification of particles having a larger size by a wet settling method.
  • Table 6 shows the results of leak test for batteries using 0.1 wt% of various indium hydroxides having different weight losses when thermally decomposed at up to 900°C added to the zinc alloys. The leak test was carried out for the batteries stored at 60°C for 45 days.
  • the indium hydroxide is preferred to have a weight loss of 18 to 30 wt% when thermally decomposed. No leak may occur with use of the indium hydroxide having a weight loss of 20 to 25 wt% even after storing at 60°C for 60 days.
  • This example concerns batteries using the combination of zinc alloys, indium hydroxide as inorganic inhibitor and a surfactant as organic inhibitor.
  • Table 7 shows the results of leak test for the batteries in which the amount of the indium hydroxide added was 0.1 wt% based on the weight of the zinc alloys and the amount of the organic inhibitor was changed. The leak test was carried out with the batteries stored at 60°C for 60 days.
  • the amount of the surfactant is preferred to be in the range of 0.001 to 0.1 wt% based on the weight of the zinc alloys.
  • Table 8 shows the results of leak test for batteries using the amount of the surfactant fixed to 0.01 wt% and the changed amounts of indium hydroxide. The leak test was carried out with the batteries stored at 60°C for 60 days.
  • Table 9 shows the results of leak test for batteries using the amount of the surfactant fixed to 0.01 wt% and the changed amounts of indium sulfide. The leak test was carried out with the batteries stored at 60°C for 75 days.
  • indium hydroxide and indium sulfide added are suitably in the range of 0.005 to 0.5 wt%.
  • Table 10 shows the results of leak test for batteries in which the amount of the surfactant was 0.01 wt% and the amount of indium hydroxide was 0.1 wt% based on the weight of the zinc alloy, and the kinds and the amounts of the alloying additives were changed.
  • the leak test was carried out with the batteries stored at 60°C for 60 days.
  • the amounts of the additives are suitably in the range of 0.01 to 1 wt% for indium, 0.005 to 0.5 wt% for each or two of lead and bismuth or 0.005 to 0.2 wt% for each or two of calcium and aluminum. Furthermore, substitution of lithium for the aluminum could obtain the same effect.
  • the surfactant used in EXAMPLE 5 was a perfluoroalkyl polyethylene oxide surfactant having the following formula of (X) - C n F 2n - (Y) - (CH2CH2O) m - (Z) wherein X is -F, Y is -C2H4-O-CH2CH(OH)-CH2O-, Z is -CH3, n is 9 and m is 60.
  • a surfactant represented by the formula of (X) - C n F 2n - (Y) - (CH2CH2O) m - (Z) wherein X is -H or -F, Y is -C2H4-O-CH2CH(OH)-CH2O-, -CONH- or -SO2NR- wherein R is -H or an alkyl group, Z is -CH3, -PO3W2 or -SO3W wherein W is an alkali metal, n is in the range of 4 to 10 and m is in the range of 20 to 100, or (X) - C n F 2n - (CH2CH2) - (CH2CH2O) m - (Z) wherein X is -H or -F, Z is -CH3, -PO3W2 or -SO3W wherein W is an alkali metal, n is in the range of 4 to 10 and m is in the range of
  • Powders of the indium hydroxide and the indium sulfide used were prepared from the sulfate as starting material and contained 80 wt% or more of the particles of the hydroxide and the sulfide having a particle size of 0.5 to 8 »m. Sufficient resistance to the electrolyte leak was confirmed to be obtained with indium hydroxide prepared from the same starting materials and having the same properties as those of EXAMPLES 2, 3 and 4 above.

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Claims (12)

  1. Verfahren zur Herstellung einer alkalischen Zinkbatterie, welches die folgenden Schritte umfaßt:
    zur Verfügung Stellen eines Zinklegierungspulvers, enthaltend wenigstens ein Legierungselement aus der Gruppe, bestehend aus Indium, Blei, Wismuth, Lithium, Kalzium und Aluminium;
    zur Verfügung Stellen von Indiumhydroxid oder Indiumsulfid, hergestellt aus einem Indiumsalz als Ausgangsmaterial durch Neutralisieren einer wässrigen Lösung dieses Salzes; und
    Dispergieren dieses Zinklegierungspulvers als ein aktives Material und des Indiumhydroxids oder Indiumsufids in einem gelartigen alkalischen Elektrolyten, um eine gelartige Anode herzustellen, wobei das Indiumhydroxid oder Indiumsulfid in einer Menge von 0,005 bis 0,5 Gew.-%, basierend auf dem Gewicht der Zinklegierung, enthalten ist.
  2. Verfahren nach Anspruch 1, worin die Zinklegierung, enthaltend 0,01 bis 1 Gew.-% Indium und insgesamt 0,005 bis 0,5 Gew.-% von einem oder beiden der Elemente Blei und Wismuth, als das aktive Anodenmaterial verwendet wird.
  3. Verfahren nach Anspruch 1, worin die Zinklegierung, enthaltend 0,01 bis 1 Gew.-% Indium, insgesamt 0,005 bis 0,5 Gew.-% von einem oder beiden der Elemente Blei und Wismuth und insgesamt 0,005 bis 0,2 Gew.-% von einem oder mehreren der Elemente Lithium, Kalzium und Aluminium, als das aktive Anodenmaterial verwendet wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, worin das Indiumsalz Indiumchlorid oder Indiumsulfat ist.
  5. Verfahren nach einem der Ansprüche 1 bis 3, worin das Indiumsalz Indiumnitrat oder Indiumsulfat ist und das Indiumhydroxid oder Indiumsulfid durch Neutralisieren einer wässrigen Lösung des Chloridionen enthaltenden Inidumsalzes hergestellt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, worin das Pulver des hergestellten Indiumhydroxids oder Indiumsulfids 60 Gew.-% oder mehr an Teilchen enthält, welche eine Teilchengröße von 0,5 bis 8 »m besitzen.
  7. Verfahren nach einem der vorhergehenden Ansprüche, worin das Indiumhydroxid einen Gewichtsverlust von 18 bis 30 Gew.-% zeigt, wenn es thermisch bei einer Temperatur von bis zu 900 °C zersetzt wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, worin das Indiumhydroxid ein Pulver-Röntgenbeugungsmuster aufweist, welches Peaks bei 4,71 ± 0,10 Å, 3,98 ± 0,02 Å, 3,57 ± 0,10 Å und 2,66 ± 0,02 Å aufweist.
  9. Verfahren nach einem der vorhergehenden Ansprüche, worin zusätzlich zu dem Indiumhydroxid oder Indiumsulfid ein Alkalimetallsulfid in einer Menge von 0,002 bis 0,2 Gew.-%, basierend auf dem Gewicht der Zinklegierung, zu dem gelartigen, alkalischen Elektrolyten zugesetzt wird.
  10. Verfahren nach einem der vorhergehenden Ansprüche, worin der alkalische Elektrolyt eine oberflächenaktive Substanz, welche einen hydrophilen Teil aus Polyethylenoxid und einen oleophilen Teil aus einer Fluoralkylgruppe aufweist, in einer Menge von 0,001 bis 0,1 Gew.-%, basierend auf dem Gewicht der Zinklegierung, enthält.
  11. Verfahren nach Anspruch 10, worin die oberflächenaktive Substanz die Formel

            (X) - CnF₂n - (Y) - (CH₂CH₂O)m - (Z)

    aufweist, worin X -H oder -F ist, Y -C₂H₄-O-CH₂CH(OH)-CH₂O-, -CONH oder -SO₂NR ist, worin R -H oder eine Alkylgruppe ist, Z -CH₃, -PO₃W₂ oder -SO₃W ist, worin W ein Alkalimetall ist, n im Bereich von 4 bis 10 ist und m im Bereich von 20 bis 100 ist, und in einer Menge von 0,001 bis 0,1 Gew. -%, basierend auf dem Gewicht der Zinklegierung, enthalten ist.
  12. Verfahren nach Anspruch 10, worin die oberflächenaktive Substanz die Formel

            (X) - CnF2n - (CH₂CH₂O)m - (Z)

    aufweist, worin X -H oder -F ist, Z -CH₃, -PO₃W₂ oder -SO₃W ist, worin W ein Alkalimetall ist, n im Bereich von 4 bis 10 ist und m im Bereich von 40 bis 100 ist, und in einer Menge von 0,001 bis 0,1 Gew.-%, basierend auf dem Gewicht der Zinklegierung, enthalten ist.
EP91108064A 1990-05-17 1991-05-17 Verfahren zur Herstellung von alkalischen Zinkbatterien Expired - Lifetime EP0457354B1 (de)

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JP128480/90 1990-05-17
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JP12848490A JPH0697611B2 (ja) 1990-05-17 1990-05-17 亜鉛アルカリ電池の製造法
JP128484/90 1990-05-17
JP12847990A JPH07107857B2 (ja) 1990-05-17 1990-05-17 亜鉛アルカリ電池の製造法
JP12848290A JPH07107858B2 (ja) 1990-05-17 1990-05-17 亜鉛アルカリ電池
JP12848090A JP2808822B2 (ja) 1990-05-17 1990-05-17 亜鉛アルカリ電池の製造法
JP128479/90 1990-05-17
JP128485/90 1990-05-17
JP2128485A JP2754865B2 (ja) 1990-05-17 1990-05-17 亜鉛アルカリ電池の製造法

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US5168018A (en) 1992-12-01
AU622588B2 (en) 1992-04-09
KR910020959A (ko) 1991-12-20
KR940007633B1 (ko) 1994-08-22
CA2042549A1 (en) 1991-11-18
EP0457354A1 (de) 1991-11-21
AU7701791A (en) 1991-11-28
CA2042549C (en) 1994-05-10
DE69111686T2 (de) 1996-03-21
DE69111686D1 (de) 1995-09-07

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